Sublimable aromatic compositions

ABSTRACT

Sublimable aromatic compositions containing triisopropyl-s-trioxane or tritertiary-butyl-s-trioxane and an additive such as perfume, which compositions, contrary to conventional sublimable materials, are characterized by their ability to contain large percentages of perfume without a drop in their melting point, enabling manufacture of superfine sublimable aromatic compositions.

This is a continuation-in-part of Serial No. 424,313, filed Dec. 13,1973, now abandoned.

The present invention relates to sublimable aromatic compositions andtheir preparation and use. It relates to sublimable aromaticcompositions comprising sublimable materials far more advantageous insublimability, aromatizability and melting point than conventionalmaterials of this kind.

Conventionally, various kinds of sublimable aromatic compositions havebeen manufactured by means of mixing non-sublimable materials such asperfume, coloring material, pigment, deodorant, and the like, orcombinations thereof, with sublimable materials such as camphor,naphthalene, p-dichlorobenzene and the like, or combinations thereof, toprepare room aromatics, toilet room deodorants, insecticides, animalrepellents, telephone receiver aromatics and the like.

These conventional sublimable materials, however, are defective in suchregards as being objectionably odorous themselves, and being liable tomelt in proportion to the amount of perfume contained therein, theirmelting point decreasing significantly in the presence of more than aminimal amount of perfume. For instance, when p-dichlorobenzene is thesublimable material, only up to 1% by weight of perfume may be mixedtherewith in regard to the foregoing effect.

The present invention obviates the foregoing defects by using twotrioxane homologues, triisopropyl-s-trioxane andtritertiary-butyl-s-trioxane, which two substances have been confirmedto be quite suitable for preparing sublimable aromatic composites bymixing them with non-sublimable materials. [These two substances will bereferred to hereinafter as trioxane (1) and trioxane (2), respectively.]

The present invention resulted from a thorough study of trioxanes (1)and (2) in a series of tests confirming said materials to be ofsublimable, odorless character, capable of admixture with a large volumeof perfume oil without a drop in their melting points. The experimentshave proven that trioxane, shown by the general formula below, isreadily sublimed, but is odorous when R = H, is an odorous liquid when R= methyl or ethyl, and only when R = isopropyl or tertiary-butyl, is itan odorless, sublimable crystal. As the result, the trioxanes (1) and(2), synthesized by means of cyclizing and trimerizing correspondingaldehydes by mineral acids, halogens, ZnCl₂, PCl₅, and the like, havebeen found to be capable of obviating the defects of conventionalsublimable materials, with the melting point being graduated at 62.5° C.in the case of trioxane (1) and 92.0° C. in the case of trioxane (2).

Formula of Trioxane: ##STR1##

The odorless character of trioxanes (1) and (2) enables them to beapplicable to any kind of aromatic, showing their extent of use to bewider than conventional sublimable materials. Furthermore, trioxanes (1)and (2) are chemically stable, free from influence, such as decomposingeffect, of other chemicals, and have no influence against additivesthereto.

The sublimable character of said materials was shown as follows:

The trioxanes (1) and (2), each molded into a disc tablet 3.0 cm indiameter and 0.23 cm thick, were left in a thermostat at variabletemperatures while maintaining the humidity at 65% ± 5% for seven days,their sublimation percentages being recorded as below (Table I), provingthat said materials are quite suitable for the manufacture of sublimablearomatic compositions.

                  Table I                                                         ______________________________________                                        Temperature (° C.)                                                                      (1) (%)     (2) (%)                                          ______________________________________                                        20 ± 1        42.2        16.9                                             30 ± 1        73.3        29.3                                             37 ± 1        98.8        39.5                                             ______________________________________                                    

As described heretofore, conventional sublimable materials, beingobjectionably odorous themselves, make it necessary to have a largecontent of perfume to cover their odors with fragrance, which isinconsistent with their inability to contain such large amounts ofperfume because of the large drop in their melting point; thepermissible content of perfume ranging only from 0.5% to 1.0% in thecase of using p-dichlorobenzene as the sublimable material.

As a countermeasure, polyvinylalcohol, CMC, cellulose, diatomaceousearth, and the like (refer to Japan Patent Publication No. 47-29536) orgelling agent have been used, the former as additives to the foregoingsublimable materials, both providing a solution to the problem of dropin melting point. They, however, have proven to be defective in thestate of prepared compositions, i.e., said additives remain unsublimedin case of using the former and become deformed or dwindle in size incase of using the gelling agent.

Compared to above described sublimable materials, trioxanes (1) and (2)are odorless, sublimable and exhibit a very small drop in melting point;that is, the melting point never drops below 50° C. even in the presenceof 15% of perfume in the case of trioxane (1), or below 65° C. in thepresence of 20% perfume in the case of trioxane (2). This enables one todecide the amount of perfume and other additives as required inaccordance with the purpose of producing the composition to be used.

To described more concretely, Jasmin OG- 100 (produced by Ogawa & Co.,Ltd.) was added to trioxanes (1) and (2) at random in various mixingratios, the mixture being heated until becoming a solution, saidsolution then being cooled. The relation between the perfume content andmelting point of trioxanes (1) and (2) was disclosed as the result,which is shown in comparison with that of p-dichlorobenzene in Table II.

As seen in Table II, trioxane (1) is able to contain perfume up to 10-15%; trioxane (2) up to 15- 20%.

In the case of trioxane (1), the composition of the present inventionpreferably contains 80- 99% by weight of trioxane (1) and 1- 20% byweight of the additive, which additive contains at least one of, forexample, a perfume, a deodorant and an insecticide. In the case oftrioxane (2), the composition of the present invention preferablycontains 75- 99% by weight of trioxane (2) and 1- 25% by weight of theadditive, which additive contains at least one of, for example, aperfume, a deodorant and an insecticide.

The following examples serve to illustrate the present invention, whichexamples are not, however, limitive of the present invention.

EXAMPLE I

Sulfuric acid, 50% in concentration, and 50 parts (parts denoteweight-parts hereinunder) by weight thereof, was cooled down to 0° C.-3° C., adding thereto 15 parts of isobutylaldehyde dropwise underagitation for one hour. 30 minutes later, 30 parts of petroleum etherwas added thereto to extract crystals separated therefrom. The petroleumether layer was separated and washed with 5% sodium bicarbonate solutionand then washed with water until said layer was neutral. The organiclayer was dried over anhydrous magnesium sulphate and then filtered torecover the petroleum ether. The residue was cooled, obtaining 10 partsof solid raw triisopropyl-s-trioxane, which was recrystallized frommethanol to obtain 9.5 parts of pure, odorless product having a meltingpoint of 62.5° C. The product proved to be equivalent to the standardcompound, based on IR and NMR spectra.

Further experiments using said crystals were conducted as follows:

EXAMPLE II

To 100 parts of triisopropyl-s-trioxane was added 10 parts of perfume(Jasmin OG- 100 of Ogawa & Co., Ltd.) under thorough mixing, theresultant mixture being punched into tablets. Said tablets proved to beof sublimable aromatic composite nature usable for room deodorization.

EXAMPLE III

To 5.0 grams of purified triisopropyl-s-trioxane was added 0.5 gram ofperfume (Rose OG- 100 of Ogawa & Co., Ltd.) under thorough mixing, themixture obtained thereby being converted to disc tablets 3.0 cm indiameter and 0.76 cm in thickness. The tablets showed no sign of meltingor deformation during storage in a thermostat keeping the temperature at50° C. ± 1° C. for a lengthy period of time. The tablets were effectiveenough to generate pleasing fragrance in a room 26.28 cubic meters incapacity.

For comparison, an experiment was carried out using, as substrate,p-dichlorobenzene in lieu of triisopropyl-s-trioxane. As in theforegoing Examples, 0.5 g of perfume (Rose OG - 100 produced by Ogawa &Co., Ltd.) was first admixed with 5.0 g of p-dichlorobenzene. Theresultant mixture was liquid at 50° C. ± 1° C., and was foundunpracticable.

EXAMPLE IV

To 100 parts of purified triisopropyl-s-trioxane was added 10 parts ofdeodorant (Cleaner OG- 1000 of Ogawa & Co., Ltd.) under thorough mixing,resulting in the production of sublimable aromatic tablets in variousshapes for commercial use.

EXAMPLE V

To 3.0 grams of purified triisopropyl-s-trioxane was added to 0.45 gramof deodorant (Cleaner OG- 2000 of Ogawa & Co., Ltd.) under thoroughmixing, the mixture thereby being molded into tablets of sublimablearomatic deodorant 3.0 cm in diameter and 0.47 cm thick. This productwas set in a flush toilet room on a wall wherein at a point one meterabove the floor, the room measuring 0.8 meter wide at the entrance, 1.15meters deep, and 2.38 meters high, and was left there in temperaturesranging from 8° C. to 12° C. for 20 days, with a panel of 10 testersstanding by in turn to observe the odorous condition of the room throughthe entire period. The testers unanimously agreed as to theeffectiveness of the product as being able to fill the room with apleasant fragrance.

EXAMPLE VI

To 20 parts of trimethyl acetaldehyde was added dropwise under stirring100 parts of 70% sulphuric acid at temperatures ranging from 5° C. to10° C. for 2 hours. The resultant mixture was left standing for anadditional one hour, and then 60 parts of petroleum ether was addedthereto, resulting in the extraction of separated crystals. After thepetroleum ether layer was separated, the mixture was neutralized with asodium carbonate aqueous solution, then dried by anhydrous magnesiumsulphate. After filtering, the petroleum ether was recovered therefrom,leaving 13 parts of raw crystals. By subjecting the raw crystals torecrystalization with methanol, 12 parts of pure white and odorlesssublimable crystals were obtained. The product, having a melting pointof 92° C., proved to be quite identical to puretritertiary-butyl-s-trioxane based on IR, NMR and Mass Spectra. Furtherexperiments were carried out with the use of this material.

EXAMPLE VII

To 20 grams of purified tritertiary-butyl-s-trioxane was added 2 gramsof perfume (Cologne OG- 400 of Ogawa & Co., Ltd.) under thorough mixing.The mixture was formed into a disc tablet 6.0 cm in diameter and 0.8 cmin thickness. The tablet was stored in a thermostat at 60° C. ± 1° C.for a lengthy period of time without showing any sign of melting orformation. The tablet was effective enough to generate a pleasantfragrance in a room of 26.2 cubic meters.

EXAMPLE VIII

To 100 parts of purified tritertiary-butyl-s-trioxane was added 15 partsof deodorant (Deodorant OG- 1000 of Ogawa & Co., Ltd.) under thoroughmixing. The mixture was molded into a toilet deodorant high in meltingpoint and rich in pleasant odor by applying a blend-melt-solidifyingprocess to the tablet.

EXAMPLE IX

To 0.5 gram of purified triteriary-butyl-s-trioxane was added 0.75 gramof aromatic deodorant (Freshner OG- 400 of Ogawa & Co., Ltd.) underthorough mixing. The mixture was molded into a disc tablet 3.0 cm indiameter and 0.78 cm in thickness. The tablet was put on a wall onemeter above the floor in a toilet room measuring 1 meter long, 2.38meters high and 0.8 meter wide maintained at a temperature of 15° C.-25° C. for 20 days. A panel of 10 testers stood by in turn to observethe odorous condition in the room, unanimously agreeing to theeffectiveness of the tablet in filling the room with a pleasantfragrance through the entire testing period.

EXAMPLE X

To 3.0 grams of triisopropyl-s-trioxane was added 0.2 gram each oflinalool, linalool oxide, anethol, cinnamic aldehyde, cinnamon oil,menthol, menthylacetate, eugenol and thymol, respectively, underthorough mixing. Each of the mixtures was punched into a disc tablet 3.0cm in diameter and 0.47 cm thick, all alike.

Twenty heads of 50-day old larvae of Tinae pellionella weighing 4.5 mgper head on the average, fed at a temperature of 20° C. ± 1° C. andhumidity of 65% ± 5%, were put in a Petri dish with flakes of 500 mgdried bonito, with a stainless wire net of 80 meshes separating the dishproper with its cover to permit the larvae to breath. The tablets werearranged separately from each other at the center of the dish, the dishmeasuring 8.5 cm in inside diameter. As the result of the test,continued at a temperature of 20° C. ± 1° C. and humidity of 65% ± 5%for 20 days, the effect of the tablets in driving out the insects wasrecorded as shown in Table III. The tablets not only showed a remarkableeffect for killing or reducing the weight of the insects but also provedto be quite free from melting and deformation.

EXAMPLE XI

Floral perfume (Perfume OG- 401 of Ogawa & Co., Ltd.) was mixed withtriisopropyl-s-trioxane dividedly in three mixing ratios, namely, 3%, 5%and 10%. 3 grams of each mixture was molded into a disc tablet 3 cm indiameter, respectively. The effect of the tablets in driving out theinsects was determined in a manner similar to that described in ExampleX, except that the larvae were fed with 500 mg of white pure wool whichhas no mothproof character. The test results, as shown in Table IV showsthat the sublimable aromatic tablets have a strong effect for killinginsects.

                  Table V                                                         ______________________________________                                         Chemicals            Quantity (%)                                            ______________________________________                                        Terpinol              1.50                                                    Phenylacetate         0.20                                                    Cinnamic Acid         0.20                                                    Eugenol               0.05                                                    Thymol                0.05                                                    Phenoxyethyl Alcohol  3.00                                                    Perfume (Floral 100 of                                                         Ogawa & Co., Ltd.)   5.00                                                    Triisopropyl-s-trioxane                                                                             90.00                                                   TOTAL                 100.00                                                  ______________________________________                                    

A composition was prepared by mixing the chemicals, as shown in Table V,and 2.5 g of the composition was molded into a ring-shaped tablet 4.0 cmin outside diameter and 2.0 cm in inside diameter. The tablet proved tobe effective as a sublimable aromatic sterilizer for telephone receiversin a test conducted in a room at 20° C. for 30 days. No sign of melting,deformation or generation of objectionable odor was observed with thetablet through the entire experiment.

Any perfume, deodorant or insecticide can be used in the composition ofthe present invention, as long as it is liquid or solid at roomtemperature.

The tradename materials referred to above are defined as follows:

    ______________________________________                                        Jasmin OG-100         % by weight                                             ______________________________________                                        Benzyl Acetate        52.5                                                    Jasmin Absolute       7.5                                                     α-Amylcinnamic Aldehyde                                                                       5.6                                                     Indole                0.2                                                     Linalool              6.7                                                     Benzyl Alcohol        7.5                                                     Benzyl Butyrate       4.7                                                     Cananga Oil           0.8                                                     Orange Oil Bitter     3.8                                                     Linalyl Acetate       4.7                                                     Methyl Anthranilate   6.0                                                     TOTAL                 100.0                                                   Cleaner OG-1000       % by weight                                             ______________________________________                                        Terpineol             28.0                                                    Hydroxycitronellal    32.0                                                    Heliotropin           8.0                                                     Linalool              4.0                                                     Phenylethyl Alcohol   8.0                                                     Phenylacetaldehyde    0.2                                                     Anis Aldehyde         0.4                                                     Benzyl Acetate        7.0                                                     Cinnamyl Alcohol      1.0                                                     Ylang - Ylang Oil     0.8                                                     Geranyl Crotonate     10.6                                                    TOTAL                 100.0                                                   Cologne OG-400        % by weight                                             ______________________________________                                        Bergamol Oil          33.0                                                    Lemon Oil             17.0                                                    Orange Oil Sweet      10.0                                                    Neroli Oil            17.0                                                    Lavender Oil          12.0                                                    Rosemary Oil          11.0                                                    TOTAL                 100.0                                                   Freshner OG-400       % by weight                                             ______________________________________                                        Phenylethyl Alcohol   28.0                                                    Rose Oil              6.0                                                     Ionone Alpha          1.0                                                     Linalool              6.0                                                     Citronellol           17.0                                                    Rhodinol              28.0                                                    Nonyl Aldehyde        1.0                                                     Hydroxycitronellal    3.0                                                     Geranyl Crotonate     10.0                                                    TOTAL                 100.0                                                   Floral 100            % by weight                                             ______________________________________                                        Methyl Ionone         16.5                                                    Ionone 100%           51.0                                                    Orris Concrete        5.0                                                     Cassia Absolute       1.0                                                     Heliotropin           6.5                                                     Bergamot Oil          3.0                                                     Violet Leaf Absolute  8.0                                                     Methyl Heptine Carbonate                                                                            1.0                                                     Anis Aldehyde         8.0                                                     TOTAL                 100.0                                                    Rose OG-100          % by weight                                             ______________________________________                                        Phenylethyl Alcohol   9.0                                                     Geraniol              40.0                                                    Rose Oil              10.0                                                    Ionone Alpha          4.0                                                     Linalool              1.5                                                     Geranyl Acetate       3.5                                                     Geranium Oil Terpeneless                                                                            6.0                                                     Eugenol               1.0                                                     Nonyl Aldehyde        0.1                                                     Nerol                 20.0                                                    Orris Oil Liquid      1.0                                                     Rhodinyl Formate      2.0                                                     Musk Ketone           0.8                                                     Undecylic Aldehyde    0.2                                                     Lauric Aldehyde       0.2                                                     Vanillin              0.7                                                     TOTAL                 100.0                                                   Cleaner OG-2000       % by weight                                             ______________________________________                                        Heliotropin           20.0                                                    Terpineol             14.0                                                    Hydroxycitronellal    4.0                                                     Phenylethyl Acetate   2.0                                                     α-Amylcinnamic Aldehyde                                                                       10.0                                                    Ionone Alpha          2.0                                                     Cinnamyl Alcohol      7.5                                                     Anisyl Alcohol        10.0                                                    Isobutyl Benzoate     14.0                                                    Lauryl Methacrylate   6.0                                                     Geranyl Crotonate     3.5                                                     Benzylidene Acetone   5.0                                                     Phenylacetaldehyde    2.0                                                     TOTAL                 100.0                                                   Deodorant OG-1000     % by weight                                             ______________________________________                                        Phenylacetaldehyde    20.0                                                    Cinnamyl Alcohol      25.0                                                    Benzyl Acetate        5.0                                                     Heliotropin           10.0                                                    Ionone Alpha          2.0                                                     Coumarin              2.0                                                     Bergamot Oil          7.0                                                     Ylang - Ylang Oil     2.0                                                     Terpineol             15.0                                                    Hydroxycinnamyl Alcohol                                                                             4.0                                                     Geranyl Crotonate     8.0                                                     TOTAL                 100.0                                                   Perfume OG-401        % by weight                                             ______________________________________                                        Linalool              15.0                                                    Linalool Oxide        10.0                                                    Cinnamon Oil          1.0                                                     Menthyl Acetate       5.0                                                     Anethol               3.0                                                     Jasmin Absolute       2.0                                                     Anisaldehyde          9.0                                                     Benzyl Acetate        40.0                                                    α-amylcinnamic Aldehyde                                                                       5.0                                                     Phenylethyl Alcohol   10.0                                                    TOTAL                 100.0                                                   ______________________________________                                    

                                      Table II                                    __________________________________________________________________________    perfume                                                                       content                                                                       (Weight                                                                       (%)     0    0.5  1    2    5    8    10   15   20                            materials                                                                     __________________________________________________________________________    (1) M.P.                                                                              62.5      61.0 58.0 56.0 54.0 52.5 51.0                               ° C        -62.0                                                                              -60.0                                                                              -58.5                                                                              -57.0                                                                              -55.5                                                                              -54.0                              (2) M.P.                                                                              92.0           87.5 82.0      71.0 68.5 66.0                          ° C             -90.0                                                                              -87.0     -80.0                                                                              -78.0                                                                              -76.0                         p-dichloro-  49.0 45.0 38.0                                                   benzene 53.0 -51.0                                                                              -47.0                                                                              -42.0                                                  __________________________________________________________________________

                                      Table III                                   __________________________________________________________________________                at the end of 20 - days testing period                                        sublimation   feeding                                                                              weight change                                                                          no. of killed                                   rate of                                                                              feeding                                                                              attack rate                                                                          of twenty Tinea                                                                        Tinea Pellionella/20                chemicals   tablet (%)                                                                           attack (mg.)                                                                         (%)    Pellionella (mg)                                                                       heads                               __________________________________________________________________________     linalool   12.5   0      0      -47.2    20                                  linalool oxide                                                                            11.2   20.6   4.1    -45.9    17                                  anethol     12.2   3.0    0.6    -47.6    20                                  cinnamic aldehyde                                                                         12.3   4.5    0.9    -35.8    20                                  cinnamon oil                                                                              10.8   6.2    1.2    -24.6    20                                  menthol     11.8   82.6   16.5   - 8.2    19                                  menthyl acetate                                                                           12.1   13.1   2.6    -45.6    20                                  eugenol     12.6   5.2    1.4    -46.0    20                                  thymol      12.3   4.1    0.8    -48.5    20                                  control (triiso-                                                              propyl-s-trioxane                                                             only)       7.6    325.0  65.0   +58.2    0                                   control (no chemicals)                                                                    --     302.9  60.6   +54.2    0                                   __________________________________________________________________________

                                      Table IV                                    __________________________________________________________________________            No. of Tinea Pellionella killed/                                                                  feeding attack                                                                        feeding attack                                    20 heads            quantity (mg)                                                                         rate (%)                                  content of           after  after   after                                     Perfume after after  twenty-three                                                                         twenty-three                                                                          twenty-three                              OG - 401 (%)                                                                          six days                                                                            fifteen days                                                                         days   days    days                                      __________________________________________________________________________    0.0 (control)                                                                         0 head                                                                               0 head                                                                               0 head                                                                              251.0   50.2                                      3.0     3 head                                                                              15 head                                                                              20 head                                                                              15.0    3.0                                       5.0     6 head                                                                              20 head                                                                              20 head                                                                              3.5     0.7                                       10.0    12 head                                                                             20 head                                                                              20 head                                                                              1.2     0.2                                       __________________________________________________________________________

We claim:
 1. An aromatic, solid, sublimable composition consisting of80-99% by weight of triisopropyl-s-trioxane and 1-20% by weight of anadditive selected from the group consisting of a perfume which is liquidat room temperature, a perfume which is solid at room temperature, adeodorant which is liquid at room temperature, a deodorant which issolid at room temperature, an insecticide which is liquid at roomtemperature, an insecticide which is solid at room temperature and amixture thereof.
 2. The composition according to claim 1, wherein theadditive is a perfume.
 3. The composition according to claim 1, whereinthe additive is a deodorant.
 4. The composition according to claim 1,wherein the additive is an insecticide.
 5. An aromatic, solid,sublimable composition consisting of 75-99% by weight oftritertiary-butyl-s-trioxane and 1-25% by weight of an additive selectedfrom the group consisting of a perfume which is liquid at roomtemperature, a perfume which is solid at room temperature, a deodorantwhich is liquid at room temperature, a deodorant which is solid at roomtemperature, an insecticide which is liquid at room temperature, aninsecticide which is solid at room temperature, and a mixture thereof.6. The composition according to claim 5, wherein the additive is aperfume.
 7. The composition according to claim 5, wherein the additiveis a deodorant.
 8. The composition according to claim 5, wherein theadditive is an insecticide.